CN116060049B - Hydrogenation catalyst and preparation method and application thereof - Google Patents

Hydrogenation catalyst and preparation method and application thereof Download PDF

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CN116060049B
CN116060049B CN202111279510.3A CN202111279510A CN116060049B CN 116060049 B CN116060049 B CN 116060049B CN 202111279510 A CN202111279510 A CN 202111279510A CN 116060049 B CN116060049 B CN 116060049B
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catalyst
metal
solution
active metal
active
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CN116060049A (en
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于秋莹
袁胜华
耿新国
隋宝宽
王永林
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a hydrogenation catalyst, a preparation method and application thereof. The preparation method comprises the following steps: (1) Preparing an active metal solution A, dipping active metal on active carbon powder, drying and roasting to obtain a metal pre-loaded carbon carrier; (2) Heating the metal pre-loaded carbon carrier in the step (1) and ammonium hypophosphite solid under vacuum to react, and keeping the two reactants out of contact; (3) Mixing the sample treated in the step (2) with pseudo-boehmite, extruding strips, and drying to obtain a catalyst precursor; (4) Mixing the catalyst precursor prepared in the step (3) with an active metal solution B, carrying out secondary impregnation, drying and roasting to obtain the catalyst. The catalyst provided by the invention has the advantages of higher metal loading, uniform dispersion, higher mechanical strength, proper pore distribution and specific surface area, and outstanding catalytic efficiency in residual oil hydrotreatment.

Description

Hydrogenation catalyst and preparation method and application thereof
Technical Field
The invention relates to a hydrogenation catalyst and a preparation method and application thereof, in particular to a residual oil hydrogenation catalyst and a preparation method and application thereof.
Background
At present, the residual oil hydrogenation catalyst mainly uses alumina or silicon dioxide as a carrier, active metal components such as Ni, mo, co and the like are loaded on the carrier through an impregnation method or a kneading method, and then the hydrogenation catalyst is obtained through high-temperature roasting. In the existing method, when the active metal load is large, the phenomenon of agglomeration or uneven distribution of metal particles is easy to occur. In addition, in the roasting process, the formation of metal-oxygen-aluminum bonds can be caused due to the strong interaction between the metal and the carrier, so that the catalytic efficiency of the catalyst is affected, and finally, the hydrogenation activity of the catalyst is reduced.
CN103055908a discloses a method for preparing a hydrotreating catalyst. Firstly pulping aluminum hydroxide or aluminum oxide to prepare slurry, and adding concentrated phosphoric acid to react to obtain sol; then taking the sol as a binder, kneading with macroporous alumina and small pore alumina, forming, drying and roasting to obtain an alumina carrier; then, the alumina carrier is impregnated with the active metal component impregnation liquid, and the hydrotreating catalyst is prepared by drying and roasting. The method takes concentrated phosphoric acid as a structural auxiliary agent, and introduces the concentrated phosphoric acid onto an alumina carrier to improve the load dispersity of active metal and reduce the total acid content of the carrier, and simultaneously can improve the pore structure of the alumina carrier.
CN105582945A discloses a method for preparing a hydrotreating catalyst. The method comprises the steps of firstly soaking an alumina carrier by urea aqueous solution, then spraying and soaking the alumina carrier by polyol or monosaccharide aqueous solution according to the sequence of the concentration from high to low, so that the concentration of the polyol and/or monosaccharide is distributed on the carrier in a gradient manner from outside to inside, and then loading active metal components. The method ensures that the subsequent active metal center has the characteristic of gradually increasing the activity from outside to inside due to the gradient distribution of the carbonized shell layers, thereby greatly reducing the blocking rate of the pore canal. However, this method requires multi-step spray impregnation to form the polymer carbonized shell layer, and has high requirements for solution concentration, and the actual operation process is complicated.
The preparation method of the hydrogenation catalyst disclosed in CN102451704A is a synthesis method of impregnating active components after mechanical mixing and molding of amorphous silica-alumina and alumina, and the hydrocracking catalyst can be obtained after drying and calcining treatment. The method avoids strong interaction between the active metal and the carrier, and the catalyst can be molded without roasting after being impregnated, although the method is favorable for uniform distribution of the metal on the carrier. But also has the defects of weaker mechanical strength of the catalyst, easy loss of metal components and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation catalyst, and a preparation method and application thereof. The catalyst provided by the invention has the advantages of higher metal loading, uniform dispersion, higher mechanical strength, proper pore distribution and specific surface area, and outstanding catalytic efficiency in residual oil hydrotreatment.
The first aspect of the invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps:
(1) Preparing an active metal solution A, dipping active metal on active carbon powder, drying and roasting to obtain a metal pre-loaded carbon carrier;
(2) Heating the metal pre-loaded carbon carrier in the step (1) and ammonium hypophosphite solid under vacuum to react, and keeping the two reactants out of contact;
(3) Mixing the sample treated in the step (2) with pseudo-boehmite, extruding strips, and drying to obtain a catalyst precursor;
(4) Mixing the catalyst precursor prepared in the step (3) with an active metal solution B, carrying out secondary impregnation, drying and roasting to obtain the catalyst.
Further, in the step (3), the preferred preparation method of the pseudo-boehmite is as follows:
(a) Respectively preparing a first aluminum-containing alkaline solution and a second aluminum-containing alkaline solution with two different alumina concentrations;
(b) Reacting the first aluminum-containing alkaline solution with a mixed gas containing carbon dioxide until the pH value of the solution is 4-6 to obtain a seed crystal solution;
(c) Adding bottom water into a reaction kettle, heating to the reaction temperature, adding the seed crystal solution in the step (b) and the second aluminum-containing alkaline solution into the reaction kettle in parallel flow for reaction, keeping the pH value constant, and aging, washing and drying after the reaction is finished to obtain the pseudo-boehmite.
Further, in the step (a), the alkaline solution containing aluminum is one or two of sodium metaaluminate solution or potassium metaaluminate solution, preferably sodium metaaluminate solution; the concentration of the first aluminum-containing alkaline solution is 40 to 100g Al 2O3/L, preferably 60 to 70g Al 2O3/L, in terms of Al 2O3. The caustic ratio of the first aluminum-containing alkaline solution is 1.1-2; the concentration of the second aluminum-containing alkaline solution is 130 to 350g Al 2O3/L, preferably 160 to 240Al 2O3/L, calculated as Al 2O3. The second aluminum-containing alkaline solution has a caustic ratio of 1.1 to 2.
Further, in the step (b), the volume fraction of carbon dioxide in the mixed gas is 10% -25%, and the mixed gas containing carbon dioxide can be a mixed gas of carbon dioxide and air; the reaction time is 1-5 min. The initial reaction temperature of the reaction carried out by introducing the mixed gas containing carbon dioxide is 15-65 ℃, the reaction is exothermic, the temperature of the system is gradually increased, the whole reaction process does not need to be cooled to keep low temperature, and the temperature of the slurry is 40-75 ℃ when the reaction is finished.
Further, in the step (c), before the parallel flow reaction, adding bottom water into the reaction kettle, wherein the bottom water accounts for 1/10-1/5 of the volume of the reaction container; the co-current reaction is carried out with stirring. The temperature of the parallel flow reaction is 40 ℃ to 75 ℃, preferably 45 ℃ to 70 ℃.
Further, in the step (c), the parallel flow feeding time of the second aluminum-containing alkaline solution is controlled to be 30-150 min.
Further, in the step (c), the second alkaline solution containing aluminum is added into the reaction kettle, and simultaneously, the first alkaline solution is added into the carbonized slurry, and the pH value of the slurry in the reaction kettle is controlled to be 8-9 by adjusting the flow rate of the slurry.
Further, in the step (c), the aging temperature is 60-90 ℃ and the aging time is 40-90 min; the washing is to wash the mixture to be neutral by water at the temperature of 60-90 ℃; the drying condition is that the drying is carried out for 4 to 10 hours at the temperature of 100 to 120 ℃.
Further, in the step (1), the specific surface area of the activated carbon is 350-480 m 2/g. The water absorption rate of the activated carbon is in the range of 0.7-1.5 mL/g.
Further, in the step (1), the impregnation method adopts saturated impregnation.
Further, in the step (1), the active metal in the active metal solution a is at least one selected from cobalt and nickel, preferably cobalt, which are metals of group VIII; the load is 30% -50% of the mass of the VIII group total active metal oxide in the catalyst in terms of oxide; wherein the concentration of the active metal solution A calculated by active metal oxide is 0.02-0.4 g/mL.
Further, in the step (1), the drying temperature is 100-120 ℃ and the drying time is 2-5 h; the roasting temperature is 400-450 ℃, inert atmosphere and/or nitrogen protection are/is introduced for 2-3 hours, and the inert atmosphere is at least one of Ar and He.
Further, in the step (2), the mass ratio of the ammonium hypophosphite to the active metal in the metal pre-loaded carbon carrier is 1-10.
Further, in the step (2), the heating temperature is 250-280 ℃ and the time is 1-2 h.
Further, in the step (2), the vacuum degree of the vacuum is-0.10-0 MPa.
Further, in the step (3), the mass ratio of the sample treated in the step (2) to the pseudo-boehmite is 0.05-0.3. An extrusion aid can be added in the extrusion process, the extrusion aid can be sesbania powder, and the addition amount of the extrusion aid is 1-6% of the mass of the pseudo-boehmite.
Further, in the step (3), the drying temperature is 80-120 ℃ and the time is 4-6 h.
Further, in the step (4), the impregnation adopts saturated impregnation; the active metal in the active metal solution B is selected from at least one of VIB group metal and at least one of VIII group metal, wherein the VIB group metal is preferably at least one of Mo and W, more preferably Mo, and the VIII group metal is preferably at least one of Co and Ni, more preferably Co.
Further, the amount of the VIII group active metal introduced into the catalyst from the step (4) accounts for 50-70% of the mass of the VIII group total active metal oxide in the catalyst in terms of oxide.
Further, in the step (4), after the twice impregnation, the mass content of the group VIB metal in the obtained catalyst is 15% -25% of the total mass of the catalyst in terms of oxide, and the mass content of the group VIII metal in the obtained catalyst is 3% -8% of the total mass of the catalyst in terms of oxide.
Further, in the step (4), the material is dried after being immersed, the drying temperature is 80-120 ℃, the drying time is 2-5 hours, and the material is baked after being dried, the baking temperature is 400-650 ℃, and the baking time is 3-5 hours.
In a second aspect the present invention provides a hydrogenation catalyst obtainable by the process according to the first aspect.
Further, in the catalyst, the active metal is at least one of group VIB metals and at least one of group VIII metals, wherein the group VIB metals are preferably at least one of Mo and W, more preferably Mo, and the group VIII metals are preferably at least one of Co and Ni, more preferably Co.
Further, in the catalyst, the active metal load is 15% -25% of the content of the VIB group metal and 3% -8% of the content of the VIII group metal based on the mass of the oxide.
Further, the catalyst also contains phosphorus, and the mass content of the phosphorus is 0.2% -2%.
Further, in the catalyst, the dispersity of the active metal is as follows: i VIB/IAl (x 100) is 8.5 to 10, and I VIII/IAl (x 100) is 4 to 5.5.
Further, the specific surface area of the catalyst is 160-225 m 2/g, preferably 179-220 m 2/g, the pore volume is 0.8-1.1 cm 3/g, the mechanical strength is 16-20N/mm, preferably 18-20N/mm, the pore volume of the pores with the pore diameter of >15nm accounts for 7.5-15% of the total pore volume, and the pore volume of the pores with the pore diameter of <8nm accounts for 7% or less, preferably 4-6.5% of the total pore volume.
Further, the acid amount of the catalyst is 0.3 to 0.6mmol/g, preferably 0.35 to 0.50mmol/g.
The third aspect of the invention provides the application of the hydrogenation catalyst in a residual oil hydrogenation process.
Further, the residuum and hydrogen-containing gas are contacted and reacted under hydrogenation reaction conditions in the presence of the residuum hydrogenation catalyst or the residuum hydrogenation catalyst obtained according to the above preparation method.
In the residual oil hydrogenation reaction, the residual oil material is selected from one of atmospheric residual oil, vacuum residual oil and high-temperature coal tar.
In the above-mentioned residuum hydrogenation reaction, the hydrogen-containing gas is hydrogen or a mixed gas of hydrogen and other gases, and the hydrogen volume content in the mixed gas is generally not less than 80%, preferably not less than 85%, and more preferably not less than 95%.
In the residuum hydrogenation process, the residuum hydrogenation operation conditions are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 280-400 ℃, the liquid hourly space velocity is 0.1-3.0 h -1, and the hydrogen-oil volume ratio is 100-1000.
Compared with the prior art, the invention has the following advantages:
Firstly, in the preparation method of the catalyst, in the first metal impregnation process, active phase VIII metal is firstly loaded on a carbon carrier, after being heated together with ammonium hypophosphite in vacuum, the ammonium hypophosphite is decomposed in a PH 3 mode, so that the VIII metal on the surface of the carbon carrier is partially phosphated to form VIII metal-P semiconductor, when the active metal is secondarily loaded, a metal-semiconductor heterojunction is formed on the contact interface between the VIII metal and the VIII metal-P semiconductor, the migration rate of electrons between metals is accelerated, the interaction force between VIII metals is enhanced, the metal dispersibility is improved, the metal loading capacity is increased, the electron migration efficiency between the active metal and an alumina carrier is greatly weakened, the adsorption and bonding effect between the active metal and the alumina carrier are weakened, and the activity of the synthesized catalyst is higher in the residual oil hydrogenation process.
Furthermore, the synthesis process of pseudo-boehmite preferably adopts the seed crystal method provided by the invention, the quick crystallization is carried out in a first reaction kettle, and pseudo-boehmite particles with larger crystal grains are continuously generated in a second reaction kettle. In the preparation method, the concentration variable range of the alkaline solution is wider, the operability is stronger, the reaction is less influenced by environmental conditions, the production efficiency is high, and the process is simple. The hydrogenation catalyst prepared from the pseudo-boehmite has higher metal dispersity, higher mechanical strength, larger pore volume and better desulfurization, nitrogen and metal performances.
Finally, the hydrogenation catalyst obtained by the invention is used for the residual oil hydrogenation reaction, shows good desulfurization, denitrification and carbon residue removal performances, and also shows excellent catalytic performances in the aspect of demetallization.
Detailed Description
The technical scheme and effect of the present invention are further described below by examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
In the invention, a nitrogen adsorption and desorption curve of a sample is tested by adopting an ASAP2020 type full-automatic physical adsorption instrument of Micromeritics company in the United states at the temperature of minus 196 ℃, and the specific surface area, pore volume and pore diameter distribution are measured.
In the invention, the mechanical strength is tested by adopting a large-connection intelligent tester for testing the strength of the intelligent particles of type ZQJ-III, and the average mechanical strength of a group of samples with the length of 4-6mm is measured.
In the invention, the metal dispersity is obtained by measuring XPS peak intensity ratio of active metal and aluminum element by XRS (Kratos Axis Ultra DLD model instrument).
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Example 1
(1) Two sodium metaaluminate solutions were prepared, the low concentration of which was 65g/L Al 2O3 solution, the caustic ratio of which was 1.15, and the high concentration of which was 160g/L Al 2O3 solution, both of which had a caustic ratio of 1.35. 3000mL of low-concentration sodium metaaluminate solution is added into the first reaction kettle, and carbon dioxide gas is introduced until the pH value of the solution is reduced to 5.5, and the reaction time is controlled within 5 min. Adding 500mL of deionized water into 5000mL of a second reaction kettle, stirring and heating, adding 800mL of high-concentration sodium metaaluminate solution into the second reaction kettle at a flow rate of 6mL/min when the temperature reaches 70 ℃, simultaneously adding carbonized slurry in parallel, controlling the pH value of the slurry in the second reaction kettle to be 8.6 constant by adjusting the flow rate of the carbonized slurry, and after the carbonized slurry is completely added, finishing the reaction, starting aging and heating, wherein the aging temperature is 90 ℃ and the time is 90min. And then washing the product fully by deionized water at the temperature of 75 ℃ and drying the product at the temperature of 120 ℃ for 6 hours to obtain the pseudo-boehmite.
(2) And (3) saturating 80mL of active metal solution with the CoO content of 0.135g/mL on 100g of active carbon powder with the specific surface area of 420m 2/g, drying for 4 hours at 110 ℃, and roasting for 3 hours at 430 ℃ under the protection of nitrogen atmosphere to obtain the metal pre-loaded carbon carrier, wherein the mass of Co introduced into the catalyst in the step (2) accounts for 31.3% of the total Co in the catalyst.
(3) Weighing 100g of the metal pre-loaded carbon carrier and 50g of ammonium hypophosphite solid, and carrying out non-contact heating reaction for 2h under the vacuum condition of 270 ℃ and minus 0.05 MPa.
(4) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(5) An impregnating solution containing MoO 3 at 0.309g/mL and CoO 0.058g/mL was prepared to saturate and impregnate the catalyst precursor, and after impregnation, the catalyst precursor was dried at 120 ℃ for 5 hours and calcined at 650 ℃ for 3 hours, thus obtaining a final hydrogenation catalyst A, the physicochemical properties of which are shown in Table 1.
Example 2
Other synthesis procedures were the same as in example 1 except that the addition amount of the ammonium hypophosphite solid was changed to 95g to obtain a final hydrogenation catalyst B, the physicochemical properties of which are shown in Table 1.
Example 3
Other synthesis procedures were the same as in example 2 except that the concentration of CoO in the impregnation solution in the first step was changed to 0.206g/mL, the concentration of MoO 3 and CoO solution in the impregnation solution in the second step was changed to 0.312g/mL, the concentration of CoO 3 was changed to 0.045g/mL, and the calcination temperature after impregnation was changed to 450 ℃ to obtain the final hydrogenation catalyst C (physical and chemical properties are shown in table 1), wherein the amount of Co introduced into the catalyst in step (2) was 46.9% of the total Co in the catalyst based on the mass of the oxide.
Example 4
Other synthesis procedures were the same as in example 1 except that the concentrations of the two sodium metaaluminate solutions were adjusted to 70g/L and 220g/L, respectively, to obtain final hydrogenation catalyst D, the physicochemical properties of which are shown in Table 1.
Comparative example 1
(1) Two sodium metaaluminate solutions were prepared, the low concentration of which was 65g/L Al 2O3 solution, the caustic ratio of which was 1.15, and the high concentration of which was 160g/L Al 2O3 solution, both of which had a caustic ratio of 1.35. 3000mL of low-concentration sodium metaaluminate solution is added into the first reaction kettle, and carbon dioxide gas is introduced until the pH value of the solution is reduced to 5.5, and the reaction time is controlled within 5 min. Adding 500mL of deionized water into 5000mL of a second reaction kettle, stirring and heating, adding 800mL of high-concentration sodium metaaluminate solution into the second reaction kettle at a flow rate of 6mL/min when the temperature reaches 70 ℃, simultaneously adding carbonized slurry in parallel, controlling the pH value of the slurry in the second reaction kettle to be 8.6 constant by adjusting the flow rate of the carbonized slurry, and after the carbonized slurry is completely added, finishing the reaction, starting aging and heating, wherein the aging temperature is 90 ℃ and the time is 90min. Then washing with 75 ℃ deionized water fully, and drying at 120 ℃ for 6 hours to obtain pseudo-boehmite.
(2) 80ML of active metal solution with the CoO content of 0.135g/mL is saturated and immersed on 100g of active carbon powder with the specific surface area of 420m 2/g, and is dried for 4 hours at 110 ℃, and then is roasted for 3 hours at 430 ℃ under the protection of nitrogen atmosphere, so as to obtain the metal pre-loaded carbon carrier. Wherein the amount of Co introduced into the catalyst in step (2) is 31.3% of the total Co in the catalyst based on the mass of the oxide.
(3) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(4) An impregnating solution containing MoO 3 at 0.309g/mL and CoO 0.058g/mL was prepared to saturate and impregnate the catalyst precursor, and after impregnation, the catalyst precursor was dried at 120 ℃ for 5 hours and calcined at 650 ℃ for 3 hours, thus obtaining a final hydrogenation catalyst E, the physicochemical properties of which are shown in Table 1.
Comparative example 2
(1) Two sodium metaaluminate solutions were prepared, the low concentration of which was 65g/L Al 2O3 solution, the caustic ratio of which was 1.15, and the high concentration of which was 160g/L Al 2O3 solution, both of which had a caustic ratio of 1.35. 3000mL of low-concentration sodium metaaluminate solution is added into the first reaction kettle, and carbon dioxide gas is introduced until the pH value of the solution is reduced to 5.5, and the reaction time is controlled within 5 min. Adding 500mL of deionized water into 5000mL of a second reaction kettle, stirring and heating, adding 800mL of high-concentration sodium metaaluminate solution into the second reaction kettle at a flow rate of 6mL/min when the temperature reaches 70 ℃, simultaneously adding carbonized slurry in parallel, controlling the pH value of the slurry in the second reaction kettle to be 8.6 constant by adjusting the flow rate of the carbonized slurry, and after the carbonized slurry is completely added, finishing the reaction, starting aging and heating, wherein the aging temperature is 90 ℃ and the time is 90min. Then washing with 75 ℃ deionized water fully, and drying at 120 ℃ for 6 hours to obtain pseudo-boehmite.
(2) 80ML of active metal solution with the CoO content of 0.284g/mL is saturated and immersed on 100g of active carbon powder with the specific surface area of 420m 2/g, and is dried for 4 hours at 110 ℃, and then is roasted for 3 hours at 430 ℃ under the protection of nitrogen atmosphere, so as to obtain the metal pre-loaded carbon carrier. Wherein the amount of Co introduced into the catalyst in step (2) is 64.5% of the total Co in the catalyst based on the mass of the oxide.
(3) Weighing 100g of the metal pre-loaded carbon carrier and 50g of ammonium hypophosphite solid, and carrying out non-contact heating reaction for 2h under the vacuum condition of 270 ℃ and minus 0.05 MPa.
(4) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(5) An impregnating solution containing MoO 3 at 0.312g/mL and CoO 0.030g/mL was prepared to saturate and impregnate the catalyst precursor, the catalyst precursor was dried at 120 ℃ for 5 hours after impregnation, and the final hydrogenation catalyst F was obtained after calcination at 650 ℃ for 3 hours, and the physicochemical properties of the final hydrogenation catalyst F are shown in Table 1.
Comparative example 3
(1) 3000ML of sodium metaaluminate solution with the concentration of 65gAl 2O3/L and the caustic ratio of 1.35 is added into a 5.0L reaction kettle, then mixed gas of carbon dioxide with the carbon dioxide content of 80% (volume fraction) and air is introduced, the initial reaction temperature is 25 ℃, the slurry temperature is kept unchanged by cooling, the reaction time is controlled to be 45min, and the pH value of the sodium metaaluminate solution is reduced to 8.8. The slurry was filtered, washed with deionized water at 75 ℃ and dried at 120 ℃ for 6 hours after the washing was completed to obtain pseudo-boehmite.
(2) 80ML of active metal solution with the CoO content of 0.135g/mL is saturated and immersed on 100g of active carbon powder with the specific surface area of 420m 2/g, and is dried for 4 hours at 110 ℃, and then is roasted for 3 hours at 430 ℃ under the protection of nitrogen atmosphere, so as to obtain the metal pre-loaded carbon carrier. Wherein the amount of Co introduced into the catalyst in step (2) is 31.3% of the total Co in the catalyst based on the mass of the oxide.
(3) Weighing 100g of the metal pre-loaded carbon carrier and 50g of ammonium hypophosphite solid, and carrying out non-contact heating reaction for 2h under the vacuum condition of 270 ℃ and minus 0.05 MPa.
(4) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(5) An impregnating solution containing MoO 3 at 0.309G/mL and CoO 0.058G/mL was prepared to saturate and impregnate the catalyst precursor, and after impregnation, the catalyst precursor was dried at 120 ℃ for 5 hours and calcined at 650 ℃ for 3 hours, thus obtaining a final hydrogenation catalyst G, the physicochemical properties of which are shown in Table 1.
Example 5
Examples 1-4 and comparative examples 1-3 were used in residuum hydrogenation reactions, respectively, with feedstock properties shown in Table 2, and evaluation conditions and results shown in Table 3.
TABLE 1 physicochemical Properties of hydrogenation catalysts
TABLE 2 oil Properties of raw materials
Density (20 ℃ C.) kg/m 3 987.5
S，wt％ 3.56
N，ppm 2426
CCR，wt％ 12.5
Ni，ppm 23.6
V，ppm 73.1
Table 3 evaluation conditions and evaluation results of the hydrogenation catalysts obtained in each example

Claims (18)

1. A method for preparing a hydrogenation catalyst, comprising the steps of:
(1) Preparing an active metal solution A, dipping active metal on active carbon powder, drying and roasting to obtain a metal pre-loaded carbon carrier;
(2) Heating the metal pre-loaded carbon carrier in the step (1) and ammonium hypophosphite solid under vacuum to react, and keeping the two reactants out of contact;
(3) Mixing the sample treated in the step (2) with pseudo-boehmite, extruding strips, and drying to obtain a catalyst precursor;
(4) Mixing the catalyst precursor prepared in the step (3) with an active metal solution B, carrying out secondary impregnation, drying and roasting to prepare the catalyst;
In the step (1), the active metal in the active metal solution a is selected from a group VIII metal, wherein the group VIII metal is metallic cobalt;
In the step (4), the active metal in the active metal solution B is selected from a group VIB metal and a group VIII metal, wherein the group VIB metal is Mo, and the group VIII metal is Co;
in the step (3), the preparation method of the pseudo-boehmite comprises the following steps:
(a) Respectively preparing a first aluminum-containing alkaline solution and a second aluminum-containing alkaline solution with two different alumina concentrations;
(b) Reacting the first aluminum-containing alkaline solution with a mixed gas containing carbon dioxide until the pH value of the solution is 4-6 to obtain a seed crystal solution;
(c) Adding bottom water into a reaction kettle, heating to the reaction temperature, adding the seed crystal solution in the step (b) and the second aluminum-containing alkaline solution into the reaction kettle in parallel flow for reaction, keeping the pH value constant, and aging, washing and drying after the reaction is finished to obtain the pseudo-boehmite.
2. The method according to claim 1, wherein in the step (1), the specific surface area of the activated carbon is 350 to 480m 2/g.
3. The preparation method according to claim 1, wherein in the step (1), the loading is 30% -50% of the mass of the total active metal oxide of the group VIII in the catalyst in terms of oxide; wherein the concentration of the active metal solution A calculated by active metal oxide is 0.02-0.4 g/mL.
4. The method according to claim 1, wherein in the step (1), the drying temperature is 100 to 120 ℃ for 2 to 5 hours; the roasting temperature is 400-450 ℃, and the inert atmosphere and/or nitrogen protection are/is introduced for 2-3 hours.
5. The method according to claim 1, wherein in the step (2), the mass ratio of the ammonium hypophosphite to the active metal in the metal-preloaded carbon carrier is 1 to 10.
6. The method according to claim 1, wherein in the step (2), the heating temperature is 250 to 280 ℃ for 1 to 2 hours.
7. The preparation method according to claim 1, wherein in the step (3), the mass ratio of the sample treated in the step (2) to the pseudo-boehmite is 0.05-0.3.
8. The method according to claim 1, wherein in the step (4), the impregnation is saturated impregnation.
9. The preparation method according to claim 1, wherein in the step (4), after the two impregnations, the mass content of the group VIB metal in the obtained catalyst is 15% -25% of the total mass of the catalyst in terms of oxide, and the mass content of the group VIII metal in the obtained catalyst is 3% -8% of the total mass of the catalyst in terms of oxide.
10. The method according to claim 1, wherein in the step (4), the impregnated product is dried at 80 to 120 ℃ for 2 to 5 hours, and the dried product is baked at 400 to 650 ℃ for 3 to 5 hours.
11. A hydrogenation catalyst obtainable by the process of any one of claims 1 to 10.
12. The hydrogenation catalyst according to claim 11, wherein in the catalyst the active metals are a group VIB metal and a group VIII metal, wherein the group VIB metal is Mo and the group VIII metal is Co; in the catalyst, the active metal load is calculated by the mass of oxide, the content of the VIB group metal is 15-25%, and the content of the VIII group metal is 3-8%.
13. The hydrogenation catalyst according to claim 12, wherein the catalyst further contains phosphorus, and the mass content of the phosphorus is 0.2% -2%.
14. The hydrogenation catalyst according to claim 11 or 12, wherein the catalyst has an active metal dispersity of: i VIB/IAl (x 100) is 8.5 to 10, and I VIII/IAl (x 100) is 4 to 5.5.
15. The hydrogenation catalyst according to claim 11 or 12, wherein in the catalyst, the specific surface area of the catalyst is 160-225 m 2/g, the pore volume is 0.8-1.1 cm 3/g, the mechanical strength is 16-20N/mm, the pore volume of the pores with the pore diameter of >15nm accounts for 7.5-15% of the total pore volume, and the pore volume of the pores with the pore diameter of <8nm accounts for 7% or less of the total pore volume; the acid amount of the catalyst is 0.3-0.6 mmol/g.
16. The hydrogenation catalyst according to claim 11 or 12, wherein in the catalyst, the specific surface area of the catalyst is 179-220 m 2/g, the mechanical strength is 18-20N/mm, the pore volume of the pores with the pore diameter of <8nm accounts for 4% -6.5% of the total pore volume; the acid amount of the catalyst is 0.35-0.50 mmol/g.
17. Use of the hydrogenation catalyst of any one of claims 11-16 in a residuum hydrogenation process.
18. The use according to claim 17, characterized in that the operating conditions for the hydrogenation of residuum are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 280-400 ℃, the liquid hourly space velocity is 0.1-3.0 h -1, and the hydrogen-oil volume ratio is 100-1000.
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